High refractive index polymeric siloxysilane compositions

ABSTRACT

Optically transparent, relatively high refractive index polymeric compositions and ophthalmic devices such as intraocular lenses, contact lenses and corneal inlays made therefrom are described herein. The preferred polymeric compositions are produced through the polymerization of one or more siloxysilane monomers or the copolymerization of one or more siloxysilane monomers with one or more aromatic or non-aromatic non-siloxy monomers, hydrophobic monomers or hydrophilic monomers.

This patent application is a divisional application of U.S. patentapplication having Ser. No. 10/000,136, filed on Nov. 2, 2001, now U.S.Pat. No. 6,908,978.

FIELD OF THE INVENTION

The present invention relates to monomers useful in the manufacture ofbiocompatible medical devices. More particularly, the present inventionrelates to siloxysilane monomers capable of polymerization orcopolymerization to form polymeric compositions having desirablephysical characteristics for use in the manufacture of ophthalmicdevices.

BACKGROUND OF THE INVENTION

Since the 1940's ophthalmic devices in the form of intraocular lens(IOL) implants have been utilized as replacements for diseased ordamaged natural ocular lenses. In most cases, an IOL is implanted withinan eye at the time of surgically removing the diseased or damagednatural lens, such as for example, in the case of cataracts. Fordecades, the preferred material for fabricating such IOL implants waspoly(methyl methacrylate) (PMMA), which is a rigid, glassy polymer.

Softer, more flexible IOL implants have gained in popularity in morerecent years due to their ability to be compressed, folded, rolled orotherwise deformed. Such softer IOL implants may be deformed prior toinsertion thereof through an incision in the cornea of an eye. Followinginsertion of the IOL in an eye, the IOL returns to its originalpre-deformed shape due to the memory characteristics of the softmaterial. Softer, more flexible IOL implants as just described may beimplanted into an eye through an incision that is much smaller, i.e.,less than 4.0 mm, than that necessary for more rigid IOLs, i.e., 5.5 to7.0 mm. A larger incision is necessary for more rigid IOL implantsbecause the lens must be inserted through an incision in the corneaslightly larger than the diameter of the inflexible IOL optic portion.Accordingly, more rigid IOL implants have become less popular in themarket since larger incisions have been found to be associated with anincreased incidence of postoperative complications, such as inducedastigmatism.

With recent advances in small-incision cataract surgery, increasedemphasis has been placed on developing soft, foldable materials suitablefor use in the manufacture of IOL implants. In general, the materials ofcurrent commercial IOLs fall into one of three categories: silicone,hydrophilic acrylic and hydrophobic acrylic.

In general, high water content, i.e., 15 percent or greater watercontent by volume, hydrophilic acrylic materials or “hydrogels,” haverelatively low refractive indexes, making them less desirable than othermaterials with respect to minimal incision size. Low refractive indexmaterials require a thicker IOL optic portion to achieve a givenrefractive power. Silicone materials may have a higher refractive indexthan high-water content hydrogels, but tend to unfold explosively afterbeing placed in the eye in a folded position. Explosive unfolding canpotentially damage the corneal endothelium and/or rupture the naturallens capsule and associated zonules. Low glass transition temperaturehydrophobic acrylic materials are desirable because they typically havea high refractive index and unfold more slowly and more controllablythan silicone materials. Unfortunately, low glass transition temperaturehydrophobic acrylic materials, which contain little or no waterinitially, may absorb pockets of water in vivo causing light reflectionsor “glistenings.” Furthermore, it may be difficult to achieve idealfolding and unfolding characteristics due to the temperature sensitivityof some hydrophobic acrylic polymers.

Because of the noted shortcomings of current polymeric materialsavailable for use in the manufacture of ophthalmic devices such as IOLs,there is a need for stable, biocompatible polymeric materials havingdesirable physical characteristics.

SUMMARY OF THE INVENTION

Soft, foldable, relatively high refractive index, polymeric compositionsof the present invention are synthesized through the polymerization ofone or more siloxysilane monomers or alternatively through thecopolymerization of one or more siloxysilane monomers with one or morearomatic or non-aromatic non-siloxy based monomers, hydrophilic monomersor hydrophobic monomers. Polymeric compositions of the present inventionare gas permeable, transparent, relatively high in strength fordurability during surgical manipulation and relatively high inrefractive index. The subject polymeric compositions are particularlywell suited for use in the manufacture of ophthalmic devices such as butnot limited to intraocular lens (IOL) implants, contact lenses,keratoprostheses, corneal rings, corneal inlays and the like.

Preferred siloxysilane monomers for use in preparing the polymericcompositions of present invention are represented by the structures ofFormula 1 and Formula 2 below:

wherein R is a polymerizable group; X is selected from the groupconsisting of C₁₋₁₀ alkylene, C₁₋₁₀ alkyleneoxy, C₆₋₃₆ arylene and C₆₋₃₆aryleneoxy; and the R₁ groups may be the same or different selected fromthe group consisting of C₁₋₁₀ alkyl, C₁₋₂₀ cycloalkyl, C₆₋₃₆ aryl, C₆₋₃₆aryl ether, C₆₋₃₆ heterocycle, C_(6–36) heterocycle with one or moresubstituents, C₁₋₁₀ alkyl ether and C₆₋₃₆ aryloxy; and u and z are thesame or different non-negative integer less than 20.

Accordingly, it is an object of the present invention to provide atransparent, biocompatible polymeric composition having desirablephysical characteristics for use in the manufacture of ophthalmicdevices.

Another object of the present invention is to provide a polymericcomposition having a relatively high refractive index.

Another object of the present invention is to provide a polymericcomposition suitable for use in the manufacture of an ophthalmicimplant.

Another object of the present invention is to provide a polymericcomposition that is relatively flexible with good clarity.

Still another object of the present invention is to provide a polymericcomposition that is relatively simple to produce.

These and other objectives and advantages of the present invention, someof which are specifically described and others that are not, will becomeapparent from the detailed description and claims that follow.

FIG. 1 shows the dependence of refractive index on water contents forcopolymers based on MPTDS and DMA.

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to siloxysilane monomers and the use ofsuch monomers to produce biocompatible polymeric compositions havingdesirable physical properties for use in the manufacture of ophthalmicdevices. The siloxysilane monomers of the present invention arerepresented generally by Formula 1 and Formula 2 below,

wherein R is a polymerizable group selected from the group consisting ofmethacrylate, acrylate, acrylamido, methacrylamido, styryl, itaconate,fumaroyl, vinyl, vinyloxy, vinyl carbamate and vinyl carbonate; X isselected from the group consisting of C₁₋₁₀ alkylene such as for examplebut not limited to methylene, propylene or heptylene, C₁₋₁₀ alkyleneoxysuch as for example but not limited to ethyleneoxy, butyleneoxy oroctyleneoxy, C₆₋₃₆ arylene such as for example but not limited tophenylene or naphthylene and C₆₋₃₆ aryleneoxy such as for example butnot limited to phenyleneoxy or naphthyleneoxy; the R₁ groups may be thesame or different selected from the group consisting of C₁₋₁₀ alkyl suchas for example but not limited to methyl, propyl or pentyl butpreferably propyl for increased stability, C₁₋₂₀ cycloalkyl such as forexample but not limited to cyclohexyl or cycloheptyl, C₆₋₃₆ aryl such asfor example but not limited to phenyl or naphthyl, C₆₋₃₆ aryl ether suchas for example but not limited to phenyl ether or naphthyl ether, C₆₋₃₆heterocycle such as for example but not limited to pyridine, quinoline,furan or thiophene but preferably pyridine to increase refractive index,C₆₋₃₆ heterocycle such as those described above with one or moresubstituents such as for example but not limited to chlorine, fluorine,amine, amide, ketone or C₁₋₃ alkyl such as for example methyl or propyl,C₆₋₃₆ aryloxy such as for example but not limited to phenyloxy ornaphthyloxy and C₁₋₁₀ alkyl ethers such as for example methyl ether orpropyl ether; y may be the same or different non-negative integer lessthan 101; and u and z are the same or different non-negative integerless than 20.

Siloxysilane monomers of the present invention represented by Formula 1and Formula 2 above, may be synthesized through a co-hydrolysis reactionwith an acid scavenger as illustrated in Scheme 1 below.

As illustrated in Scheme co-hydrolysis of 1,3-methacryloyloxypropylchlorosilane with chlorophenyldimethylsilaneusing N,N-dimethylaminopyridine (DMAP) as an acid scavenger produces3-methacryloyloxypropyltris(phenyldimethylsiloxy)silane.

Examples not intended to be limiting of siloxysilane monomers of thepresent invention produced as described above include for example butare not limited to m-vinylbenzyltris(trimethylsiloxy)silane,p-vinylbenzyltris(trimethylsiloxy)silane,m-vinylbenzyltris(dimethylphenyl-siloxy)silane,p-vinylbenzyltris(dimethylphenylsiloxy)silane,3-methacryloyloxy-propyltris(triphenylsiloxy)silane,3-(triphenylsilyl)propyl vinyl ether, 3,3-diphenyl propyl maleimide,2-bromobenzyl-4-ethenylphenylether,(3-phenyldimethylsilylpropyl)-4-ethenylphenylether and3-acryloyloxypropyl-1,1-diphenyl-(2-naphthyl)silane.

Although one or more siloxysilane monomers of the present invention maybe polymerized or copolymerized to form crosslinked three-dimensionalnetworks, one or more crosslinking agents may be added thereto inquantities less than 10 percent weight per volume (W/V) if desired priorto polymerization or copolymerization thereof.

Examples of suitable crosslinking agents include but are not limited todiacrylates and dimethacrylates of triethylene glycol, butylene glycol,neopentyl glycol, ethylene glycol, hexane-1,6-diol and thio-diethyleneglycol, trimethylolpropane triacrylate, N,N′-dihydroxyethylenebisacrylamide, diallyl phthalate, triallyl cyanurate, divinylbenzene;ethylene glycol divinyl ether, N,N′-methylene-bis-(meth)acrylamide,sulfonated divinylbenzene and divinylsulfone.

Although not required, siloxysilane monomers within the scope of thepresent invention may optionally have one or more strengthening agentsadded thereto prior to polymerization or copolymerization, preferably inquantities of less than about 80 weight percent but more typically fromabout 20 to about 60 weight percent.

Examples of suitable strengthening agents are described in U.S. Pat.Nos. 4,327,203, 4,355,147 and 5,270,418 each incorporated herein in itsentirety by reference. Specific examples, not intended to be limiting,of such strengthening agents include cycloalkyl acrylates andmethacrylates, such as for example tert-butylcyclohexyl methacrylate,isopropylcyclopentyl acrylate and tert-butylcyclohexyl acrylate.

One or more ultraviolet light absorbers may optionally be added to thesubject monomers prior to polymerization or copolymerization inquantities typically less than 2 percent W/V. Suitable ultraviolet lightabsorbers for use in the present invention include for example but arenot limited to β-(4-benzotriazoyl-3-hydroxyphenoxy)ethyl acrylate,4-(2-acryloyloxyethoxy)-2-hydroxybenzophenone,4-methacryloyloxy-2-hydroxybenzophenone,2-(2′-methacryloyloxy-5′-methylphenyl)benzotriazole,2-(2′-hydroxy-5′-methacryloyloxyethylphenyl)-2H-benzotriazole,2-[3′-tert-butyl-2′-hydroxy-5′-(3″-methacryloyloxypropyl)phenyl]-5-chlorobenzotriazole,2-[3′-tert-butyl-5′-(3″-dimethylvinylsilylpropoxy)-2′-hydroxyphenyl]-5-methoxybenzotriazole2-(3′-allyl-2′-hydroxy-5′-methylphenyl)benzotriazole,2-[3′-tert-butyl-2′-hydroxy-5′-(3″-methacryloyloxypropoxy)phenyl]-5-methoxybenzotriazole,and2-[3′-tert-butyl-2′-hydroxy-5′-(3″-methacyloyloxypropoxy)phenyl]-5-chlorobenzotriazolewherein β-(4-benzotriazoyl-3-hydroxyphenoxy)ethyl acrylate is thepreferred ultraviolet light absorber.

The siloxysilane monomers of the present invention produced as describedabove may be polymerized alone or copolymerized with other monomers. Thesubject siloxysilane monomers may be copolymerized with one or morearomatic or non-aromatic non-siloxy-based monomers, hydrophobicmonomers, hydrophilic monomers or a combination thereof to producepolymeric compositions of the present invention.

Examples of aromatic and non-aromatic non-siloxy-based monomers usefulfor copolymerization with one or more siloxysilane monomers of thepresent invention include for example but are not limited to2-phenyloxyethyl methacrylate, 3,3-diphenylpropyl methacrylate, glycerylmethacrylate, 3-phenylpropyl acrylate, N,N-dimethylacrylamide, methylmethacrylate, 2-(1-naphthylethyl methacrylate) and 2-(2-naphthylethylmethacrylate) but preferably 2-(1-naphthylethyl methacrylate) forincreased refractive index.

Examples of hydrophobic monomers useful for copolymerization with one ormore siloxysilane monomers of the present invention include for examplebut are not limited to 2-ethylhexyl methacrylate,3-methacryloyloxypropyldiphenylmethylsilane and 2-phenyloxyethylmethacrylate but preferably 3-methacryloyloxypropyldiphenylmethylsilanefor increased refractive index.

Examples of hydrophilic monomers useful for copolymerization with one ormore siloxysilane monomers of the present invention include for examplebut are not limited to N,N-dimethylacrylamide and N-methylacrylamide butpreferably N,N-dimethylacrylamide for increased hydrophilicity.

The physical and mechanical properties of copolymers produced fromsiloxysilane monomers of the present invention are set forth below inTable 1.

TABLE 1 Mechanical and physical property results for films based on3-(3- methacryloyloxypropyl)-1,1,1-triphenyl-3,3-dimethyldisiloxane(MPTDS) or the acrylate (APTDS). Mod Tear % Composition W/W % R.I.(g/mm²) (g/mm) H₂O MPTDS/Dar 100/0.5 1.54 0 MPTDS/DMA/Eg/54/40/3.2/2.2/20 1.49 1703 35 28 Dar/Hex 56/42/.4/1.5/20 1.46 337 54 4364/33/2/1/20 1.51 4333 112 23 APTDS/Dar 100/0.5 1.54 0 APTDS/DMA/Eg/70/30/1/0.5/20 1.524 251 64 17 Dar/Hex 60/40/1/0.5/20 1.49 78 24 30APTDS/DMA/ 65/35/20/1/0.5 1.52 121 37 19 Hex/Eg/Irg R.I. = RefractiveIndex Mod = Modulus Eg = Egdma = Ethylene glycol dimethacrylate DMA =Dimethylacrylamide Hex = Hexanol Dar = Darocur ™ 1173 (EM Industries)Irg = Irgacure ™ 819 (Ciba-Geigy, Basel, Switzerland)

No water content, low water content of less than 15 percent watercontent by volume and high water content “hydrogels” of 15 percent orhigher water content by volume polymeric compositions of the presentinvention having ideal physical characteristics for ophthalmic devicemanufacture are described herein.

The polymeric compositions of the present invention are of relativelyhigh refractive index of approximately 1.45 or greater and relativelyhigh elongation of approximately 100 percent or greater. The polymericcompositions of the present invention with the desirable physicalproperties noted above are particularly useful in the manufacture ofophthalmic devices such as but not limited to relatively thin, foldableintraocular lens implants, contact lenses and corneal inlays.

IOLs having relatively thin optic portions are critical in enabling asurgeon to minimize surgical incision size. Keeping the surgicalincision size to a minimum reduces intraoperative trauma andpostoperative complications. A relatively thin IOL optic portion is alsocritical for accommodating certain anatomical locations in the eye suchas the anterior chamber and the ciliary sulcus. IOLs may be placed inthe anterior chamber for increasing visual acuity in either aphakic orphakic eyes, or placed in the ciliary sulcus for increasing visualacuity in phakic eyes.

The polymeric compositions of the present invention have the flexibilityrequired to allow implants manufactured from the same to be folded ordeformed for insertion into an eye through the smallest possiblesurgical incision, i.e., 3.5 mm or smaller. It is unexpected that thesubject polymeric compositions could possess the ideal physicalproperties described herein. The ideal physical properties of thesubject polymeric compositions are unexpected since high refractiveindex monomers typically lend to polymers with increased crystallinityand decreased clarity, which is not true in the case of the subjectpolymeric compositions.

The subject siloxysilane monomers and polymeric compositions producedtherefrom are described in still greater detail in the examples thatfollow.

EXAMPLE 1

Synthesis of MPTDS

To a 1000 ml one-neck round bottom flask fitted with a magnetic stirrer,condenser, heating mantle and nitrogen blanket, was added 500 ml CHCl₃,18.2 grams (149 mmol) of dimethylaminopyridine (DMAP), 37.6 grams (135.9mmol) of triphenylsilanol and 30.0 grams (135.9 mmol) of3-methacryloyloxypropyldimethylchlorosilane.

The contents of the flask were refluxed for 72 hours and then allowed tocool to room temperature. The organics were washed twice in 500 ml 2NHCl, then dried over magnesium sulfate and flashed to an oil. Aftercolumn chromatography on silica gel eluting with 80.0% heptane and 20.0%CH₂Cl₂, the product was isolated. The chromatography was monitored bythin layer chromatography (TLC) plates.

EXAMPLE 2

To 64 parts of MPTDS was added 33 parts of dimethylacrylamide, 20 partsof hexanol, 2 parts of ethyleneglycol dimethacrylate and 1.0% ofIrgacure™ 819 as the UV photoinitiator and 0.25% of a commercialtriazole UV blocker (Aldrich Chemical Co). The clear solution wassandwiched between two silanized glass plates using metal gaskets andexposed to UV radiation for two hours. The resultant films were releasedand extracted in isopropanol (IPA) for four hours, followed byair-drying and a 30 mm vacuum to remove the IPA. The resultant film washydrated at room temperature overnight in borate buffered saline. Theclear tack-free films possessed a modulus of 4333 g/mm², a tear strengthof 112 g/mm, a water content of 23% and a refractive index of 1.51.

EXAMPLE 3

To 70 parts of APTDS was added 30 parts of dimethylacrylamide, 20 partsof hexanol, 1 part of ethyleneglycol dimethacrylate and 0.5% ofIrgacure™ 819 as the UV photoinitiator and 0.25% of a commercialtriazole UV blocker (Aldrich Chem. Co). The clear solution wassandwiched between two silanized glass plates using metal gaskets andexposed to UV radiation for two hours. The resultant films were releasedand extracted in IPA for four hours, followed by air-drying and a 30 mmvacuum to remove the IPA. The resultant film was hydrated at roomtemperature overnight in borate buffered saline. The clear tack-freefilms possessed a modulus of 251 g/mm², a tear strength of 64 g/mm, awater content of 17% and a refractive index of 1.52.

EXAMPLE 4

To 70 parts of APTDS was added 10 parts of dimethylacrylamide, 20 partsof hexanol, 1 part of ethyleneglycol dimethacrylate and 0.5% ofIrgacure™ 819 as the UV photoinitiator and 0.25% of a commercialtriazole UV blocker (Aldrich Chem. Co). The clear solution wassandwiched between two silanized glass plates using metal gaskets andexposed to UV radiation for two hours. The resultant films were releasedand extracted in IPA for four hours, followed by air-drying and a 30 mmvacuum to remove the IPA. The resultant film was hydrated at roomtemperature overnight in borate buffered saline. The clear tack-freefilms possessed a water content of 10% and a refractive index of 1.53.

The siloxysilane monomers of the present invention may be readily curedin cast shapes by one or more conventional methods. Such methods includefor example but are not limited to ultraviolet light (UV)polymerization, visible light polymerization, microwave polymerization,thermal polymerization, free radical polymerization, living radicalpolymerization or combinations thereof. Metallocene catalysts may alsobe used in certain instances.

One or more suitable free radical thermal polymerization initiators maybe added to the monomers of the present invention. Examples of suchinitiators include but are not limited to organic peroxides, such asacetyl peroxide, lauroyl peroxide, decanoyl peroxide, stearoyl peroxide,benzoyl peroxide, tert-butyl peroxypivalate, peroxydicarbonate, and thelike. Preferably such an initiator is employed in a concentration ofapproximately 0.01 to 1 percent by weight of the total monomer mixture.

Representative UV initiators include those known in the field such asfor example but not limited to benzoin methyl ether, benzoin ethylether, Darocur™ 1173, 1164, 2273, 1116, 2959, 3331 (EM Industries) andIrgacur™ 651 and 184 (Ciba-Geigy, Basel, Switzerland).

Ophthalmic devices such as but not limited to IOLs made of the polymericcompositions of the present invention can be of any suitable design orform. For example, ophthalmic devices such as IOLs typically comprise anoptic portion and one or more haptic portions. Once implanted within aneye, the IOL optic portion reflects light onto the retina of the eye andthe permanently attached haptic portions hold the optic portion inproper alignment within the eye. The haptic portions may be integrallyformed with the optic portion in a one-piece design or attached bystaking, adhesives or other methods known to those skilled in the art ina multipiece design.

The subject ophthalmic devices, such as for example IOLs, may bemanufactured to have an optic portion and haptic portions made of thesame or differing materials. Preferably, in accordance with the presentinvention, both the optic portion and the haptic portions of the IOL aremade of the same polymeric composition of the present invention.Alternatively however, the IOL optic portion and haptic portions may bemanufactured from different materials and/or different formulations ofthe polymeric compositions of the present invention, such as describedin detail in U.S. Pat. Nos. 5,217,491 and 5,326,506, each incorporatedherein in its entirety by reference. Once the particular material ormaterials are selected, the same is either cast in molds of the desiredform and cured, or cast in the form of rods and cured. If cast in theform of rods, the rods while in a dry state are machined or lathed intodisks. The resultant disks may then be machined or lathed into IOLs orother ophthalmic devices. The IOLs or other ophthalmic devices whethermolded or machined/lathed are then cleaned, polished, hydrated, packagedand sterilized by customary methods known to those skilled in the art.

In addition to IOLs, the polymeric compositions of the present inventionare also suitable for use as other ophthalmic devices such as but notlimited to contact lenses, keratoprostheses, capsular bag extensionrings, corneal inlays, corneal rings and like devices.

IOLs and like ophthalmic devices manufactured using the unique polymericcompositions produced from the unique siloxysilane monomers of thepresent invention are used as customary in the field of ophthalmology.For example, in a surgical procedure, an incision is placed in thecornea of an eye. Most commonly through the corneal incision the naturallens of the eye is removed (aphakic application) such as in the case ofa cataractous natural lens. An IOL or the like is then inserted into theanterior chamber, posterior chamber or lens capsule of the eye prior toclosing the incision. However, the ophthalmic devices of the subjectinvention may be used in accordance with other surgical procedures knownto those skilled in the field of ophthalmology.

While there is shown and described herein certain siloxysilane monomersand polymeric compositions of the present invention, it will be manifestto those skilled in the art that various modifications may be madewithout departing from the spirit and scope of the underlying inventiveconcept and that the same is not limited to particular structures hereinshown and described except insofar as indicated by the scope of theappended claims.

1. A method of producing ophthalmic devices from a polymericcomposition, said method comprising: casting said polymeric compositionin the form of a rod; lathing or machining said rod into disks; andlathing or machining said disks into said ophthalmic devices; whereinsaid polymeric composition is a polymerization product of a siloxysilanemonomer that has a formula of

wherein R is a polymerizable group; X is selected from the groupconsisting of C₁₋₁₀ alkylene, C₁₋₁₀ alkyleneoxy, C₆₋₃₆ arylene and C₆₋₃₆aryleneoxy; the R₁ groups are the same or different selected from thegroup consisting of C₁₋₁₀ alkyl, C₁₋₂₀ cycloalkyl, C₆₋₃₆ aryl, C₆₋₃₆aryl ether, C₆₋₃₆ heterocycle, C₆₋₃₆ heteroycle with one or moresubstituents, C₁₋₁₀ alkyl ether and C₆₋₃₆ aryloxy; and each of u and zis an independently chosen integer, and 1≦u, z<20.
 2. The method ofclaim 1 wherein said polymerization product is a copolymer of saidsiloxysilane monomer and one or more aromatic or non-aromaticnon-siloxy-based monomers.
 3. The method of claim 1, wherein saidpolymeric composition is a copolymer of said siloxysilane monomer andone or more aromatic or non-aromatic non-siloxy-based monomers.
 4. Themethod of claim 1, wherein said polymeric composition is a copolymer ofsaid siloxysilane monomer and one or more hydrophobic monomers.
 5. Themethod of claim 1, wherein said polymeric composition is a copolyrmer ofsaid siloxysilane monomer and one or more hydrophilic monomers.
 6. Amethod of producing ophthalmic devices from a polymeric composition,said method comprising: pouring said polymeric composition into a moldprior to curing; curing said polymeric composition; and removing saidpolymeric composition from said mold following curing thereof; whereinsaid polymeric composition is a polymer comprising units of asiloxysilane monomer that has a formula of

wherein R is a polymerizable group; X is selected from the groupconsisting of C₁₋₁₀ alkylene, C₁₋₁₀ alkyleneoxy, C₈₋₃₈ arylene and C₆₋₃₆aryleneoxy, the R₁ groups are the same or different selected from thegroup consisting of C₁₋₁₀ alkyl, C₁₋₂₀ cycloalkyl, C₆₋₃₆ aryl, C₆₋₃₆aryl ether, C₆₋₃₆ heterocycle, C₈₋₃₈ heterocycle with one or moresubstituents, C₁₋₁₀ alkyl ether and C₈₋₃₈ aryloxy; each of u and z is anindependently chosen integer; and 1≦u, z<20.
 7. The method of claim 6,wherein said polymer is a copolymer of said siloxysilane monomer and oneor more aromatic or non-aromatic non-siloxy-based monomers.
 8. Themethod of claim 6, wherein said polymer is a copolymer of saidsiloxysilane monomer and one or more aromatic or non-aromaticnon-siloxy-based monomers.
 9. The method of claim 6, wherein saidpolymer is a copolymer of said siloxysilane monomer and one or morehydrophobic monomers.
 10. The method of claim 6, wherein said polymer isa copolymer of said siloxysilane monomer and one or more hydrophilicmonomers.